Praseodymium and nickel co-doped Co3O4 enhances oxygen evolution reaction performance via interfacial water optimization and cobalt pre-oxidation for proton exchange membrane water electrolysis

doi:10.1016/S1872-2067(26)65109-1

Abstract

Abstract:

Spinel Co₃O₄ is theoretically predicted as a promising cost-effective anodic electrocatalyst for proton exchange membrane water electrolysis (PEMWE) owing to favorable adsorption energetics. However, the inevitable surface reconstruction under operating conditions severely compromises its long-term activity and stability. Here we report a praseodymium (Pr) and nickel (Ni) co-doped cobalt spinel (PrNi-Co₃O₄) catalyst featuring a spatially selective distribution of uniform bulk Ni doping and spontaneous surface Pr segregation, which realizes a surface-interface synergistic optimization strategy to effectively overcome this bottleneck. Density functional theory calculations and voltammetric investigations reveal that the nickel dopants induce surface pre-oxidation, boosting intrinsic activity while simultaneously increasing the energy for lattice cobalt leaching. Besides, in-situ surface-enhanced infrared absorption spectroscopy demonstrates that surface praseodymium species lowers the water dissociation barrier by decreasing the hydrogen bonding degree, while simultaneously reinforcing stability through the mitigation of metal-oxygen bond polarization and the anchoring of oxygenated intermediates. The assembled PEMWE cell employing the PrNi-Co₃O₄ anode operates at only 2.02 V at 1 A cm⁻² and sustains stable operation for 490 h, placing it at the forefront of reported non-noble metal catalysts. This study helps advance the commercial viability and scalability of green hydrogen production by circumventing the reliance on precious iridium.

Key words: Interfacial water, Pre-oxidation, Spinel oxide, Non-noble metal, Proton exchange membrane water electrolysis

Lingtong Ji, Peimeng Qiu, Qingjun Ma, Peng Li, Shengli Chen. Praseodymium and nickel co-doped Co₃O₄ enhances oxygen evolution reaction performance via interfacial water optimization and cobalt pre-oxidation for proton exchange membrane water electrolysis[J]. Chinese Journal of Catalysis, 2026, 90: 253-263.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65109-1

https://www.cjcatal.com/EN/Y2026/V90/I11/253

Figures/Tables 5

Fig. 1. Characterizations of structure for PrNi-Co3O4 catalyst. (a) Synthesis illustration of the PrNi-Co3O4 catalysts. (b,c) XRD patterns of Co3O4, Ni-Co3O4 and PrNi-Co3O4 catalysts. TEM images of the PrNi-Co3O4 catalyst (d) with the corresponding particle size distribution (e) and the marked lattice spacing (f). (g) EDS elemental mapping images of the PrNi-Co3O4. (h) Co, Ni and Pr atomic ratio depth profiles determined by XPS with Ar+ beam etching. Quantification was performed using only the Pr 3d3/2 and Ni 2p3/2 peaks to avoid spectral interference from Co 2s and Auger signals. (i) Variation of the Co/Pr atomic ratio with etching time.

Fig. 2. Chemical and structural characterizations. High-resolution XPS spectra of the Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts in the O 1s (a), Co 2p (b), Ni 2p (c), and Pr 3d (d) regions. Raman spectra (e) of the Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts, along with the calculated peak intensity ratios (f) of the A1g and F2g(1) modes.

Fig. 3. Electrocatalytic performance in a three-electrode system. Geometric area-normalized CV curves (a), corresponding Tafel plots (b), EIS plots (c), Cdl plots (d), and chronopotentiometric curves (e) of Co3O4, Ni-Co3O4, and PrNi-Co3O4.

Fig. 4. OER mechanism and stability analysis. (a) iR-corrected CV curves of Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts. (b) Percentage evolution of different types of interfacial water structures on Co3O4, Ni-Co3O4, and PrNi-Co3O4 as a function of applied potential. In-situ SEIRAS spectroscopy analysis of Co3O4 (c), Ni-Co3O4 (d) and PrNi-Co3O4 (e) in 0.5 mol L−1 H2SO4 at different applied potentials. (f) Atomistic structures showing the demetallation of Co from PrNi-Co3O4 surface. Pink, green, blue, and red spheres represent Co, Ni, Pr and O atoms, respectively. (g) Calculated Co demetallation energies on Co3O4 (311), Ni-Co3O4 (311), and PrNi-Co3O4 (311) surfaces.

Fig. 5. Electrochemical performance in a PEMWE cell. (a) Schematic illustration of the PEMWE cell system. (b) Current-voltage polarizations of the PEMWE cell with Co3O4, Ni-Co3O4 and PrNi-Co3O4 anodic catalyst. (c) Evolution of PEMWE polarization curves recorded after selected cycle numbers during the voltage-cycling AST. The inset illustrates the square-wave voltage protocol alternating between 1.8 and 2.0 V. (d) Variations in PEMWE cell voltage measured at different current densities every 1000 cycles during the AST. (e) Chronoamperometric stability measurement of the PrNi-Co3O4 anode at 0.1 and 1 A cm−2.

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Praseodymium and nickel co-doped Co₃O₄ enhances oxygen evolution reaction performance via interfacial water optimization and cobalt pre-oxidation for proton exchange membrane water electrolysis

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